天津地区土壤环境中有机氯农药残留特征

通过对天津市辖区6种不同土地利用类型和2种灌溉类型的188个点位进行野外实地采样及定量分析,分析了天津市土壤环境中有机氯农药(OCPs)残留的空间分布特征及来源,系统研究了天津市六六六(HCHs)和滴滴涕(DDTs)各异构体单体在土壤中的残留水平、空间和剖面的分布特征,以及残留量今昔情况比较。结果表明:天津市土壤环境中HCHs和DDTs含量均可以达到国家一级标准。天津市HCHs污染空间分布特征为近郊区、滨海地区相对较重,市区次之,远郊区较轻;DDTs污染空间分布特征为近郊区、市区相对较重,远郊区次之,滨海地区较轻;不同的土壤利用类型中,城市绿地的OCPs残留量最高,清灌区和污灌区的OCPs残留量差异不大。剖面分析结果显示,有机氯农药的残留总量主要集中在0~30 cm的耕作层中。通过比较HCHs和DDTs的残留情况发现,DDTs的降解率高于HCHs,天津个别地区出现残留水平异常情况。     

滇池流域农田土壤有机氯农药残留特征

在滇池流域农田,重点是滇池滨湖区和入滇河流柴河流域,选择不同土地利用类型、不同种植年限大棚采集土壤样品进行气相色谱（ECD）分析。结果表明,试区土壤中有机氯农药（OCPS）检出率为95.9%,OCPS的残留量范围、平均值分别为nd-63.4 μg·kg-1、6.3 μg·kg-1,以p,p′-DDE为主要残留物,98.3%的样点达到国家《土壤环境质量标准》一级标准（〈50 μg·kg-1）。与国内同类报道相比,滇池周边土壤中OCPS的残留较低。不同土地利用类型有机氯残留量排序为：设施栽培〉水稻田〉露天菜地〉荒草地〉坡耕地;不同大棚种植年限土壤中,棚龄长于15 a的 OCPS残留量要明显高于棚龄短于15 a的,而棚龄短于15 a的,土壤中OCPS含量差异不明显。     

唐山市土壤中有机氯农药的初步研究

采用加速溶剂萃取技术——气相色谱法,初步研究了唐山市区不同类型土壤中有机氯农药的成分及其含量,并对有机氯农药进行了溯源分析。结果表明所测的4种类型的土壤中六六六(HCHs)和滴滴涕(DDTs)均有检出,HCHs的平均含量为15.015ng·g-1,DDTs的平均值含量为66.4ng·g-1,均大大高于20世纪70年代我国有机氯农药使用量最大的棉田土壤中的残留量11.68ng·g-1和0.80ng·g-1。土壤中有机氯农药的高残留应该与唐山地震后喷洒大量有机氯农药有密切关系。     

水稻土中有机氯农药残留测定方法比较

研究国标方法对土壤中有机氯农药六六六、DDT 残留的测定结果,并与美国国家环境保护总局USEPA 8080 方法进行比较。结果表明,本研究条件下 USEPA 8080 方法对土壤中有机氯农药残留的测定结果显著高于国标方法,但 USEPA 8080 方法测定结果仅比国标方法测定结果高 14%,可以认为两种方法都适用于一般性的研究。     

辽东与山东半岛土壤中有机氯农药残留特征研究

2005—2008年在辽东半岛和山东半岛15个市县采集了265个土壤样品,对其10种有机氯农药进行了分析,研究该地区土壤中硫丹、HCH和DDT残留情况及其空间分布特征。结果表明,山东半岛土壤中硫丹残留量为6.30μg kg-1,为辽东半岛的9倍;HCHs残留量为4.82μg kg-1,为辽东半岛的1.3倍;辽东半岛土壤中DDTs残留量为45.70μg kg-1,为山东半岛的2.5倍。山东半岛α-HCH、p,p′-DDE、p,p′-DDT的检出率均高于80%,辽东半岛β-HCH、p,p′-DDE检出率均高于80%。不同种植方式,辽东半岛土壤OCPs残留量:果园玉米地菜地草地水稻田;山东半岛土壤OCPs残留量:果园菜地玉米地麦田棉田。与国内其他地区相比,该地区硫丹残留量相对较低,HCHs和DDTs残留量超过国家《土壤环境质量标准》(GB15618-2008)一级标准的土壤样品分别占样品总数的4.53%和9.05%。     

不同施肥方式下土中有机氯农药的残留特征

Soil samples with three fertilization treatments (no fertilizer, corn straw and farm manure) collected from a Lou soil (Eum-orthic Anthrosol classfied using Chinese Soil Taxonomy) in northwestern China were analysed for residual levels and their characteristics of organochlorine pesticides (α-HCH, β-HCH, γ-HCH, δ-HCH, HCB, o,p'-DDT, p,p'-DDT, o,p'-DDE, p,p'-DDE, p,p'-DDD, a-endosulfan, dieldrin and endrin). Organochlorine pesticides (OCPs) were detected in all soil samples except δ-HCH and their total concentrations ranged from 159.31 ± 9.00 to 179.77 ± 2.58 ng g^-1 with an order of HCHs > DDTs > (dieldrin + endrin) > HCB > α-endosulfan. Among all the compounds, γ-HCH had the highest concentration followed by p,p'-DDE. The residual levels of HCH isomers and DDT as well as their metabolites in soil with different fertilization treatments were in the order of γ-HCH > β-HCH ≈ α-HCH > δ-HCH and p,p'-DDE > p,p'-DDT > o,p'-DDT > p,p'-DDD ≈ o,p'-DDE, respectively. DDE/DDT ratios ranged from 1.59 ±0.13 to 3.35 ± 0.16 and endrin/dieldrin ratios from 1.40 ± 0.06 to 9.20 ± 4.05, both indicating no new occurrence of these pesticides in these soils, while α-HCH/γ-HCH ratios of 0.04 indicated a new input of lindane (almost pure γ-HCH) in the past several years. The farm manure treatments showed lower DDT residues than samples without fertilizer. Also addition of corn straw and farm manure increased soil organic matter content and decreased the soil pH which could retard the degradation of DDT in the soil.     

有机氯农药残留对土壤环境的影响

1993～1999年间,经对不同类型、不同耕作的土壤和农作物中有机氯农药残留的分析,阐述有机氯农药残留对土壤和农产品质量造成潜在的影响,为当前农业生产结构调整,提出相应的防治对策。     

丹江口水库淅川淹没区农田土壤中有机氯农药的分布特征及生态风险研究

采集了丹江口淅川淹没区高程在170 m以下8个乡镇的农田土壤共18个样品,采用索氏提取分离富集、气相色谱-电子捕获（GC-ECD）检测、气相色谱仪-质谱（GC-MS）确证的方法对样品中20种有机氯农药进行了分析,研究了丹江口水库淅川淹没区土壤中OCPs的分布特征与潜在风险。结果表明,研究区农田土壤中有α-HCH和DDE两种有机氯农药被检出,其中α-HCH含量范围是nd～107.55 ng·g-1,平均值为40.31 ng·g-1;DDE含量范围是1.42～237.56 ng·g-1,平均值为36.28 ng·g-1。总有机氯含量范围为15.16～279.93 ng·g-1,平均值为76.59 ng·g-1;与其他地区比较,ΣHCHs含量偏高,ΣDDTs含量相当;α-HCH可能来自早期残留,也可能来自大气沉降,DDE可能源自早期残留。淅川淹没区农田土壤中α-HCH和DDE含量基本上符合国家土壤环境质量标准一级标准,土壤质量良好,但仍然存在一定的生态风险。     

不同种源延胡索及土壤中有机氯农药残留特征及安全评价

以万州、开县实验基地土壤和9个种源延胡索为研究对象,使用气相色谱–电子捕获检测器(GC-ECD)检测了土壤和延胡索中有机氯农药(OCPs)残留量,分析其残留特征和生态安全。结果表明:①在土壤和延胡索样品中均检出了滴滴涕(DDTs)和六六六(HCHs),DDTs的检出率分别为100%和83.3%,HCHs的检出率分别为72.2%和100%。DDTs和HCHs残留量具有较大的离散性和一定的区域差异性。②在土壤样品中,检出率较高的是4,4'-DDE和α-HCH,分别为100%和66.7%。4,4'-DDE和α-HCH是OCPs残留的主要成分。③在延胡索样品中,检出率较高的是α-HCH、4,4'-DDE和β-HCH,分别为100%、77.8%和55.6%,3种成分占OCPs残留量的73.7%。延胡索对α-HCH和4,4'-DDE有很强的生物富集作用,富集因子分别约为1.8和0.65。④实验基地土壤OCPs残留符合《土壤环境质量标准》二级标准,属于尚清洁水平,延胡索的OCPs残留量符合《药用植物及制剂外经贸委绿色行业标准》。     

吉林省典型工农业地区多介质样品中有机氯农药和多氯联苯分布特征

采用气相色谱-电子捕获检测器分析了吉林省典型工农业地区表层土壤、水稻、玉米及稻田水样品中包括HCHs、DDTs在内的有机氯农药（OCPs）和7种多氯联苯（PCBs）指示性单体的含量。结果表明,表层土壤中OCPs（HCHs＋DDTs）平均含量排序为梅河口夏季（98.9ng·g-1）〉长春市（81.2ng·g-1）〉吉林市（72.6ng·g-1）〉梅河口秋季（25.2ng·g-1）,PCBs排序为梅河口夏季（98.7ng·g-1）〉长春市（平均61.0ng·g-1）〉吉林市（50.3ng·g-1）〉梅河口秋季（27.1ng·g-1）,梅河口土壤中PCBs异构体中以PCB28和PCB52为主;DDTs含量较高的地区为吉林市和长春市,其旱地土壤有利于DDTs的残留;所有水稻籽粒样品中均检出了HCHs和DDTs残留,水稻和玉米中HCH和DDTs的残留均低于国家食品卫生标准的限值,水稻秧苗和玉米秆茎样品中∑7PCBs含量都分别高于水稻和玉米籽粒样品中∑7PCBs含量;水稻田水中OCPs含量都低于国家地表水质标准限值。     

漳州土壤中有机氯农药残留研究

A soil survey was conducted in Zhangzhou City,an important agricultural region in south of the Fujian Province,China.93 surface soil samples were collected in the paddy fields,vegetable lands,orchards and tea plantations from Zhangzhou City.An additional soil profile was sampled in a paddy field as previous research had indicated high concentrations of organochlorine pesticides(OCPs) in the paddy fields.Dichlorodiphenyltrichloroethanes(DDTs) ranged from 0.64-78.07 ng g 1 dry weight and hexachlorocyclohexanes(HCHs) ranged from 0.72-30.16 ng g 1 dry weight in the surface soil of the whole study region.Ratios of α-HCH/γ-HCH < 4 and o,p-DDT/p,p-DDT > 1 in all soil samples suggested that lindane and dicofol were widely applied in this region in the past.Concentrations of HCHs and DDTs in soils from the four land use types followed the orders:paddy fields > vegetable lands > tea plantations > orchards and tea plantations > orchards > paddy fields > vegetable lands,respectively.Analyses of the data showed no correlation(r < 0.1) between elevation and OCPs contents in paddy fields,orchards and vegetable lands,indicated no significantly different features in distribution of HCHs and DDTs in the soils from low lying plains and mountains and the unsystematic usage of OCPs,and highlighted the fragmented nature of agricultural production in Zhangzhou,as well as the reemission of OCPs from the soils,where high OCPs concentrations were found,in Longhai of Zhangzhou.In addition,no obvious relationship between the OCPs and total organic carbon(TOC)(r < 0.3) was observed in the soil profile.The mean contribution of dicofol in total DDTs was 66% in the whole Zhangzhou region.The approximate burdens of HCHs and DDTs in the surface layer of 0-20 cm were 0.44 and 1.55 t,respectively.The storage of both HCHs and DDTs in soil surface layer(0-20 cm) accounts for 40% burden of the soil layer of 0-50 cm(1.10 t HCHs and 3.87 t DDTs),in which the highest concentrations of OCPs were observed in soil profile.     

Fate and plant uptake of persistent organic pollutants in soil

Many persistent organic pollutants (POPs), notably hexachlorocyclohexanes (HCHs), chlorinated cyclodienes, and dichlorodiphenyltrichloroethanes (DDTs), remain in Japanese farming soils, more than 40 years after their use as insecticides was prohibited. In recent years, residues of chlorinated cyclodienes in cucurbit fruits have become a problem. But, though HCHs and DDTs have been staying in the soil, residues of these chemicals in crops have not been a problem. So we compared the fates of HCHs (α-, β-, γ-HCHs), chlorinated cyclodienes (dieldrin, endrin, heptachlor exo-epoxide), and DDTs (DDE, dichlorodiphenyldichloroethylene; DDD, dichlorodiphenyldichloroethane) in soil and investigated their uptake by several non-cucurbits and cucurbits. As for the fate of POPs in soil, not only the total concentrations but also the concentrations in soil solution as bioavailable POPs were determined. The half-lives of total β-HCH and DDTs in soil were the longest, and α- and γ-HCHs the shortest. On the other hand, the half-lives of bioavailable POPs ranged from 1/3 to 1/20 of those of total POPs. The ratio of the half-lives of bioavailable POPs to those of total POPs decreased in the order of HCHs > chlorinated cyclodienes > DDTs. Because hydrophobic chemicals were adsorbed strongly to the soil, the bioavailable POPs in soil are controlled by their hydrophobicity, indicated by the values of log K _OW (K _OW: n-octanol-water partition coefficient). The shoot concentrations of chlorinated cyclodienes and DDTs were higher in cucurbits than in non-cucurbits. However, among POP insecticides, HCHs did not show clear differences. As for the root concentrations, all tested POPs were higher in cucurbits than in non-cucurbits. Through the determination of POPs in soil solution, we could compare the abilities of plants to take up the chemicals using soil solution bioconcentration factors (BCF_SS). The values of BCF_SS increased with the magnitude of log K _OW, in the order of HCHs < chlorinated cyclodienes < DDTs. In addition, BCF_SS did not show marked differences among isomers or chemicals with similar structure. Therefore, plant uptake ability was influenced mainly by log K _OW. After being applied to agricultural land, α- and γ-HCHs seemed to disappear quickly, β-HCH persisted longer but the uptake in roots was low because of the low log K _OW, and DDTs also persisted longer but the bioavailability decreased rapidly in the soil because of their high log K _OW. Chlorinated cyclodienes have remained in the soil and have remained available, because they are less likely than HCHs (except β-HCH) to disappear and less likely than DDTs to become adsorbed to the soil. In addition, their higher log K _OW than that of HCHs makes them more easily taken up by roots. However, shoot concentrations were high only in cucurbits, for which they remain a problem in Japan.     

滇池周边大棚土壤中六六六和滴滴涕残留特征

采用气相色谱(ECD)对滇池周边不同年限大棚土壤中六六六(HCHs)和滴滴涕(DDTs)残留量进行了测定, 探讨其残留分布特征。结果表明: (1)大棚种植年限对土壤中残留量影响显著, 种植年限长于10 年的大棚土壤中HCHs 和DDTs 的残留量显著高于年限短于10 年的大棚, DDTs 是有机氯农药(OCPs)的主要组成成分;短于10 年的大棚间, 土壤中HCHs 和DDTs 残留量差异不显著。(2)不同土层中, HCHs 残留量在土壤剖面上的变化趋势不明显, 而DDTs 在表层土壤(0~20 cm)中残留量显著高于下层。(3)从HCHs 和DDTs 的同系物组成来看, HCHs 以β-HCH 残留量最高, 部分样点中p,p′-DDT/(DDD+DDE)比值大于1。可判断HCHs 残留主要是过去施用的残留物, 而DDTs 仍有新的污染输入, 有待进一步调查研究。     

Vertical distribution of lead and arsenic in soils contaminated with lead arsenate pesticide residues

Many deciduous fruit tree orchard sites throughout the world are contaminated with lead (Pb) and arsenic (As) from past use of lead arsenate insecticides. The vertical distribution of Pb and As was examined in six contaminated orchard soils in the State of Washington, USA. Most of the Pb and As was restricted to the upper 40 cm of soil, with Pb concentration maxima ranging from 2.15 to 10.69 mmol/kg, and As concentration maxima ranging from 0.77 to 4.85 mmol/kg. In all cases, there were lower Pb and As concentrations at the soil surface than deeper in the profile. Arsenic was depleted relative to Pb in the topsoils and was enriched relative to Pb in the subsoils, suggesting that there has been preferential movement of As. Absolute soil enrichment with Pb occurred to depths between 15 and 50 cm. Absolute soil enrichment with As occurred to depths between 45 and > 120 cm. At 120 cm, Pb concentrations were < 0.05 mmol/kg, and As concentrations ranged from 0.07 to 0.63 mmol/kg. The deeper movement of Pb and As in the study soils relative to that reported for lead arsenate-contaminated soils elsewhere is attributed to high loading rates of lead arsenate, coarse soil texture, low organic matter content, and use of irrigation. The results indicate that Pb and As concentrations in lead arsenate-contaminated soils are high enough to be of potential environmental concern. The amount of As redistribution appears to be substantial enough to preclude some methods of remediation and to create potential risk of contamination of underlying shallow groundwater.     

福建茶园土壤六六六和滴滴涕残留水平及来源分析

采用现场采样及室内测试方法,分析了福建茶园土壤中六六六（HCHs）和滴滴涕（DDTs）类有机氯农药（OCPs）的分布、组成和来源。结果表明,∑HCHs和∑DDTs浓度分别为0.251-1.120 ng.g^-1和0.210-2.406 ng.g^-1,属于清洁背景范围;漳浦、福鼎和福州茶园土壤∑OCPs浓度显著高于其他样点。除福州外,其他样点HCH同系物中γ-HCH相对含量最高,占HCHs总量的26.3%-76.3%。DDTs中以o,p′-DDT相对含量最高,为34.7%-60.8%。0-15 cm土壤HCHs和DDTs浓度（分别为0.593 ng.g^-1和1.340 ng.g^-1）均高于15-30 cm（0.451 ng.g^-1和0.862 ng.g^-1）。除福州β-（/α＋γ）-HCH和α-/γ-HCH值较高外,其他样点均较低,表明福州HCHs为历史污染,其他样点均存在HCHs新输入,并可能存在林丹的使用或输入;除福鼎p,p′-DDE/p,p′-DDT值较高外,其他样点均较低,表明除福鼎外其他样点均有DDTs的新输入;o,p′-DDT/p,p′-DDT值均较高,表明可能有大量三氯杀螨醇的使用或输入。     

福州地区不同土地利用类型土壤中六六六和滴滴涕的残留特征

采集福州地区106个表层土壤样品,运用气相色谱-电子捕获检测器（GC-μECD）,分析了不同土地类型土壤中六六六（HCHs）和滴滴涕（DDTs）残留水平、组成特征及来源。结果表明,福州土壤HCHs总浓度为0.581～66.9μg·kg-1,DDTs总浓度为0.782～110μg·kg-1。不同土地利用类型土壤中HCHs残留量为未利用地〉水田〉旱田〉草地〉林地。4种HCHs异构体中,草地、旱田和林地土壤中分别以α-HCH、β-HCH和γ-HCH相对含量最高,水田和未利用地土壤中δ-HCH含量最高。不同土地利用类型土壤中DDTs残留量为未利用地〉旱田〉水田〉林地〉草地,除未利用地土壤中相对含量最高的同系物是p,p′-DDD外,其余4种类型土壤中均是p,p′-DDE相对含量最高。来源分析表明,福州可能有林丹（主要成分为γ-HCH）输入,草地可能还有工业HCHs的输入;未利用地、旱田、林地土壤还存在新的DDTs输入,水田和草地土壤近期无工业DDTs输入;旱田、水田、未利用地可能还有少量三氯杀螨醇的使用或输入。     

福建茶园茶叶中六六六和滴滴涕残留水平及来源分析

运用气相色谱-电子捕获检测器（GC-μECD）分析了福建茶园茶叶中六六六（HCHs）和滴滴涕（DDTs）等有机氯农药（OCPs）的分布、组成和来源。结果表明,∑OCPs浓度为0.764～10.561ng.g-1,永泰最高,福鼎最低,一般而言,老叶中∑OCPs浓度高于嫩叶;∑HCHs浓度为0.373～7.427ng.g-1,永泰最高,政和最低,老叶中HCHs浓度显著高于嫩叶;茶叶中HCHs同系物以γ-HCH为主,占总量的51.3%～94.1%;α-/γ-HCH表明所有茶园均存在林丹的使用或输入,β-（/α＋γ）-HCH表明所有茶园均非HCHs历史污染,可能存在HCHs其他新的来源。∑DDTs浓度为0.123～5.168ng.g-1,政和最高,福鼎最低,老叶和嫩叶中无显著差异;与土壤类似,茶叶中DDTs同系物以p,p′-DDT和o,p′-DDT为主,两者之和占总量的67.3%～96.0%;p,p′-DDE/p,p′-DDT表明,除福鼎、永泰和安溪外,其他茶园均存在工业DDTs的使用或输入;o,p′-DDT/p,p′-DDT表明,除政和外,其他茶园均存在大量的三氯杀螨醇的使用或输入,以安溪较为严重。     

典型潮土剖面主要性质和微量金属垂直分布特征

对不同利用方式下石灰性潮土剖面主要性质和微量金属元素含量垂直分异规律进行了初步研究。结果表明,长期耕种的菜地和旱地0～15cm表层土壤有机碳含量高于其他土层,pH和CaCO3含量低于下层土壤;表层土壤Cd已明显积累;但Cd、Pb、Cu、Zn含量均未超过国家土壤环境质量二级标准。几种微量金属全量在菜地和旱地表层土壤之间没有显著差异,但菜地表层土壤DTPA可提取态Cd含量显著高于旱地。从微量金属的剖面分布看,石灰性潮土全量Cd和DTPA可提取态Cd、Pb、Cu、Zn均有明显的表聚现象,这种分布与土壤有机碳含量、pH和CaCO3含量显著相关。聚类分析表明,该区域耕作土壤环境分析样品的采集以表层土壤0～15cm多点混合样品为宜。     

Vertical distribution of soil mites (Acari) in conventional and no-tillage agricultural systems

Summary Soil mite abundance was measured at four depths (0–5, 6.5–11.5, 13–18, and 19.5–24.5 cm) in agricultural plots under no-tillage or conventional tillage in Clarke County, Georgia, USA. The vertical distribution of mites was not significantly different between the two tillage systems: Most mites were found in the top 0–5 cm zone. This was the zone where greater moisture content occurred, and (in other studies) was the zone of maximum root biomass and microbial activity. Among mite suborders, only the Prostigmata were found in any abundance below 5 cm. Mite populations declined dramatically on occasions when the soil moisture exceeded field capacity, but did not appear to migrate vertically.Dedicated to the late Prof. Dr. W. Kühnelt